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We analyze the stability of anodically electrodeposited cobalt hydroxide films during operation as electrocatalysts for water oxidation and show that the stability considerations of these films are...

Co encapsulated in N-doped carbon nanotubes (Co-NCNT) catalysts are of high interest as bifunctional electrocatalyst material for both efficient oxygen evolution and reduction (OER/ORR) in applications of rechargeable metal-air batteries. Up to now, the role played by the functional metal species in OER/ORR is still insufficiently understood. The main focus of our research is to shed light on the mechanistic role of the Co species that serve as active sites in the bi-functional Co-NCNT catalysts. It is found that S700 exhibits an outstanding OER/ORR activity. We thus hypothesize that CoII and CoIII clusters predominately function as active sites in the OER and ORR processes, respectively. Furthermore, OER/ORR activity for Co-NCNT catalyst primarily correlates to eg occupation. A near-unity occupancy of the eg orbital of S700 is revealed to be the cause for the maximum intrinsic OER/ORR activity, which provides guidelines for the design of highly active catalysts.

The oxygen evolution reaction (OER) is pivotal in sustainable fuel production. Neutral-pH OER reduces operational risks and enables direct coupling to electrochemical CO2 reduction, but typically is hampered by low current densities. Here, the rate limitations in neutral-pH OER are clarified. Using cobalt-based catalyst films and phosphate ions as essential electrolyte bases, current–potential curves are recorded and simulated. Operando X-ray spectroscopy shows the potential-dependent structural changes independent of the electrolyte phosphate concentration. Operando Raman spectroscopy uncovers electrolyte acidification at a micrometer distance from the catalyst surface, limiting the Tafel slope regime to low current densities. The electrolyte proton transport is facilitated by diffusion of either phosphate ions (base pathway) or H3O+ ions (water pathway). The water pathway is not associated with an absolute current limit but is energetically inefficient due to the Tafel-slope increase by 60 mV dec−1, shown by an uncomplicated mathematical model. The base pathway is a specific requirement in neutral-pH OER and can support high current densities, but only with accelerated buffer-base diffusion. Catalyst internal phosphate diffusion or other internal transport mechanisms do not limit the current densities. A proof-of-principle experiment shows that current densities exceeding 1 A cm−2 can also be achieved in neutral-pH OER.

Nickel-based catalysts accomplish the direct conversion of urea to pure hydrogen via electrochemical oxidation; yet mechanistic understanding is lacking. Synthesizing a series of carbon fiber paper (CFP) supported Ni(OH)2/MnO2 catalysts, we explored relevant redox transitions and catalysis of both UOR (urea oxidation reaction, in KOH-with-urea) and OER (oxygen evolution reaction, in KOH). Cyclic Voltammetry (CV) in KOH-only solution demonstrated a more cathodic transformation from Ni(III/IV) to Ni(II) compared with that in KOH-with-urea solution. The water oxidation overpotential was shifted to higher values (from 0.48 to 0.53 VRHE) as the Mn:Ni atom ratio increases in CFP-NiMn films. In contrast, a higher Mn content results in higher UOR activity and lower onset potential in KOH solution containing urea (1.395–1.375 VRHE). Quasi in-situ, freeze-quench X-ray absorption spectroscopy (XAS) at the Ni and Mn K-edges was employed to uncover oxidation state changes as well as structural transformations at the atomic level showing that CFP-Ni(OH)2 underwent oxidation state changes by about 1.15 e− and 0.21 e− per Ni ion during OER and UOR processes, respectively, versus only 0.71 e− and 0.07 e− per Ni ion in CFP-NiMn2.4. Mn incorporation can stabilize the Ni in lower valent states in a mixed NiMn catalyst without significant changes in oxidation state and structure. The here investigated, readily synthesized CFP-NiMn films exhibit opposite activity trends in KOH and KOH-with-urea electrolytes: Mn incorporation depresses water oxidation, but it promotes the urea oxidation process. We propose that the water oxidation rate (OER) is positively correlated with the capacity for accumulation of Ni and Mn oxidation equivalents, while the urea oxidation (UOR) rate is negatively correlated with this capacity. Our work offers a mechanistic guideline for designing and synthesizing nonprecious metal-coupled Ni-based catalysts with appropriate redox-properties for urea-oxidation applications.

Direct (photo)electrochemical production of non-fossil fuels from water and CO2 requires water-oxidation catalysis at near-neutral pH in the presence of appropriate anions that serve as proton acceptors. We investigate the largely enigmatic structural role of anions in water oxidation for the prominent cobalt-phosphate catalyst (CoCat), an amorphous and hydrated oxide material. Co3([(P/As)O]4)2·8H2O served, in conjunction with phosphate–arsenate exchange, as a synthetic model system. Its structural transformation was induced by prolonged operation at catalytic potentials and probed by X-ray absorption spectroscopy not only at the metal (Co), but for the first time also at the anion (As) K-edge. For initially isostructural microcrystals, anion exchange determined the amorphization process and final structure. Comparison to amorphous electrodeposited Co oxide revealed that in CoCat, the arsenate binds not only at oxide-layer edges, but also arsenic substitutes cobalt positions within the layered-oxide structure in an unusual AsO6 coordination. Our results show that in water oxidation catalysis at near-neutral pH, anion type and exchange dynamics correlate with the catalyst structure and redox properties. Universidad de Costa Rica/[]/UCR/Costa Rica Consejo Nacional para Investigaciones Científicas y Tecnológicas/[]/CONICIT/Costa Rica Ministerio de Ciencia, Tecnología y Telecomunicaciones/[]/MICITT/Costa Rica German Federal Ministry of Education and Research/[]/BMBF/Alemania Deutsche Forschungsgemeinschaft/[]/DFG/Alemania UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Básicas::Centro de Investigación en Electroquímica y Energía Química (CELEQ) UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Básicas::Centro de Investigación en Ciencia e Ingeniería de Materiales (CICIMA)

Neodymium oxide (Nd2O3) nanoparticles were chemically embedded on a state-of-the art carbon felt (CF) by a precipitation method in non-aqueous solution. Different Nd2O3 loadings were chosen and the obtained electrocatalyst-loaded felts tested for application as electrode in all-vanadium redox flow batteries. Cyclic voltammetry (CV) studies confirmed that Nd2O3 has a catalytic effect towards both redox couples, V4+/V5+ at the positive and V2+/V3+ at the negative side. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD) demonstrated only minor particle agglomeration and high dispersion of the particles on the fibres. Charge/discharge profiles revealed an enhanced performance with higher discharge capacity and higher energy efficiency for the modified felts when compared to a thermally activated CF. For instance, after 50 consecutive charge/discharge cycles the energy efficiency of the Nd2O3 modified carbon felt (Nd2O3-CF) was reduced only by 3% compared to a 12% irreversible loss observed for the thermally activated CF. After exchanging the electrolyte after 50 cycles, the felts retained their original performance indicating that less degradation occurred in the modified felts than in the industrial standard and that they maintained their oxygen-donating functionalities on the surface as compared to thermally activated CF.

Catalysis of the oxygen evolution reaction (OER) by earth-abundant materials in the near-neutral pH regime is of great interest as it is the key reaction for non-fossil fuel production. To address the pertinent stability problems and insufficiently understood structure–activity relations, we investigate the influence of moderate annealing (100–300 °C for 20 min) for two types of electrodeposited Mn oxide films with contrasting properties. Upon annealing, the originally inactive and structurally well-ordered Oxide 1 of birnessite type became as OER active as the non-heated Oxide 2, which has a highly disordered atomic structure. Oxide 2 also improved its activity upon heating, but more important is the stability improvement: the operation time increased by about two orders of magnitude (in 0.1 M KPi at pH 7). Aiming at atomistic understanding, electrochemical methods including quantitative analysis of impedance spectra, X-ray spectroscopy (XANES and EXAFS), and adapted optical spectroscopies (infrared, UV-vis and Raman) identified structure–reactivity relations. Oxide structures featuring both di-μ-oxo bridged Mn ions and (close to) linear mono-μ-oxo Mn3+–O–Mn4+ connectivity seem to be a prerequisite for OER activity. The latter motif likely stabilizes Mn3+ ions at higher potentials and promotes electron/hole hopping, a feature related to electrical conductivity and reflected in the strongly accelerated rates of Mn oxidation and O2 formation. Poor charge mobility, which may result from a low level of Mn3+ ions at high potentials, likely promotes inactivation after prolonged operation. Oxide structures related to the perovskite-like ζ-Mn2O3 were formed after the heating of Oxide 2 and could favour stabilization of Mn ions in oxidation states lower than +4. This rare phase was previously found only at high pressure (20 GPa) and temperature (1200 °C) and this is the first report where it was stable under ambient conditions.

CO

The dramatic change in electrochemical behavior of nickel (oxy)hydroxide films upon incorporation of Fe ions provides an opportunity to establish effective electrocatalyst design principles. We characterize a photochemically deposited series of Fe-Ni (oxy)hydroxides by X-ray absorption spectroscopy and track the voltage- and composition-dependence of structural motifs. We observe a trigonal distortion in di-m-hydroxo bridged NiII-NiII motifs that is preserved following a symmetric contraction of Ni-O bond lengths when oxidized to di-m-oxo NiIV-NiIV. Incorporation of Fe ions into the structure generates di-m-hydroxo NiII-FeIII motifs in which Ni-Fe distances are dependent on nickel oxidation state, but Fe-O bond lengths are not. This asymmetry minimizes the trigonal distortion in di-m-hydroxo NiII-FeIII motifs and neighboring di-m-hydroxo NiII-NiII sites in the reduced state, but exacerbates it in the oxidized state. We attribute both the Fe-induced anodic shift in nickel-based redox peaks and the improved ability to catalyze the oxygen evolution reaction to this inversion in geometric distortions. Spectroelectrochemical experiments reveal a previously unreported change in optical absorbance at ca. 1.5 V vs. RHE in Fe-containing samples. We attribute this feature to oxidation of nickel ions in di-m-hydroxo NiII-FeIII motifs, which we propose is the process relevant to catalytic oxygen evolution.

Selective conversion of CO2 into high quality chemical feedstock and fuels represents an emerging energy storage technology1. The electrochemical reduction of carbon dioxide using renewable sources of energy is a promising way of utilizing the only intermittently available renewable energies to produce chemical feedstocks and fuels for later use. Presently, copper is the one metal in focus because of its ability to catalyze CO2 reduction towards energy-dense hydrocarbon products. However, the electrochemical reduction of CO2 on copper results in many different products at a wide range of overpotentials. The selectivity and efficiency of the Cu-based catalysts towards specific products can be improved by fine tuning the structure and composition2-4. In this work, high surface area porous Cu films were electrodeposited either on Cu or Pt substrates at various deposition currents and durations using the dynamic hydrogen bubble template method5. During electrodeposition at high current values, the size and residence time of H2 bubbles vary based on the substrate and on the in-situ deposited Cu, leading to significantly different catalyst morphologies. Consequently, well-defined dendritic structures with large pores are observed (inset of Fig. 1) for Cu deposited on Cu substrate (CuCat/Cu) as compared to Cu deposited on Pt substrate (CuCat/Pt). Interestingly, product quantification by gas chromatography during electrochemical measurements showed that the product selectivity observed for all variations of the catalysts deposited on a particular substrate does not depend significantly on the differences in pore size and film thickness of the material. However there is a difference in product selectivity for the respective catalysts deposited on different substrates as represented in Fig. 1, where ethylene and carbon-monoxide selectivities are shown at two different potentials. The formation of methane is significantly suppressed (I 2O species with no evidence of CuIIO species. The morphological changes, atomic state and composition of the catalyst may have a dialectic role in deciding the selectivity. In the follow-up work, the selectivity of various Cu films electrodeposited on both the substrates will be correlated with respect to surface area and CuI 2O content after comprehensive quantification of the gaseous and liquid reaction products by gas chromatography, liquid gas chromatography and HPLC. These studies are expected to reveal strategies by which catalysts can be designed for higher selectivity towards a specific hydrocarbon product. References M. Gattrell, N. Gupta and A. Co, J. Electroanal. Chem., 594, 1 (2006). 2. A. Dutta, M. Rahaman, N. C. Luedi, M. Mohos and P. Broekmann, ACS Catal. 6, 3804 (2016). H. Mistry, A. S. Varela, C. S. Bonifacio, I. Zegkinoglou, I. Sinev, et. al, Nat. Commun., 7, 12123 (2016). A. S. Varela, C. Schlaup, Z. P. Jovanov, P. Malacrida, S. Horch, et. al, J. Phys. Chem. C, 117, 20500 (2013). H. -C. Shin, J. Dong and M. Liu, Adv. Mater ., 15, 1610 (2003). Figure 1

Tetraphenylselenurane has been isolated and structurally characterized by a single crystal structure determination. (a = 1752.1(7), b = 99.6(), c = 1074.2(4) pm, s = 98.97(1)°, P21/c) It is a yellow crystalline material that explodes on warming to room temperature. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:576–578, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20686

CO2 reduction is of significant interest for the production of nonfossil fuels. The reactivity of eight Cu foams with substantially different morphologies was comprehensively investigated by analysis of the product spectrum and in situ electrochemical spectroscopies (X-ray absorption near edge structure, extended X-ray absorption fine structure, X-ray photoelectron spectroscopy, and Raman spectroscopy). The approach provided new insight into the reactivity determinants: The morphology, stable Cu oxide phases, and *CO poisoning of the H2 formation reaction are not decisive; the electrochemically active surface area influences the reactivity trends; macroscopic diffusion limits the proton supply, resulting in pronounced alkalization at the CuCat surfaces (operando Raman spectroscopy). H2 and CH4 formation was suppressed by macroscopic buffer alkalization, whereas CO and C2 H4 formation still proceeded through a largely pH-independent mechanism. C2 H4 was formed from two CO precursor species, namely adsorbed *CO and dissolved CO present in the foam cavities.